Fungicidal compositions

ABSTRACT

A novel fungicidal composition comprising a fungicidally effective amount of a combination consisting of (A) the known aminomethyl heterocycle of the formula and (B) at least one other known fungicidally active compound selected from the group mentioned in the specification. The novel compositions show a synergistic activity.

This is a division of application Ser. No. 08/989,044, filed on Dec. 11,1997, now U.S. Pat. No. 5,965,593, which is a division of applicationSer. No. 08/787,599, filed on Jan. 22, 1997, now U.S. Pat. No.5,736,551, which is a division on application Ser. No. 08/646,788, filedon May 21, 1996, now U.S. Pat. No. 5,639,774, which is a division ofapplication Ser. No. 08/432,741, filed on May 2, 1995, now U.S. Pat. No.5,569,656, which is a division of application Ser. No. 08/249,511, filedon May 26, 1994, now U.S. Pat. No. 5,439,926.

The present invention relates to novel combinations of active compounds,which combinations consist of the known8-t-butyl-2-(N-ethyl-N-n-propylamino)-methyl-1,4-dioxaspiro[4.5]decaneon the one hand and of further, known, fungicidal active compounds onthe other, and are very well suited for controlling fungi.

It is already known that8-t-butyl-2-(N-ethyl-N-n-propylamino)-methyl-1,4-dioxaspiro[4.5]decanepossesses fungicidal properties (cf. EP-OS (European PublishedSpecification) 0 281 842). The activity of this compound is good;however, in many cases it leaves something to be desired when being usedin small quantities.

It is also already known that many azole derivatives, aryl benzylethers, benzamides, morpholine compounds, and other heterocycles, can beemployed for controlling fungi (cf. K. H. Buichel "Pflanzenschutz undSchadlingsbekampfung" (Plant Protection and the Control of Pests), pages140-153, Georg Thieme-Verlag, Stuttgart 1977, EP-OS (European PublishedSpecification) 0 040 345, DE-OS (German Published Specification) 2 324010, DE-OS (German Published Specification) 2 201 063, EP-OS (EuropeanPublished Specification) 0 112 284, EP-OS (European PublishedSpecification) 0 304 758 and DD-PS (East German Patent Specification 140412).

Fungicidal combinations of active compounds consisting of8-t-butyl-2-(3,5-dimethylpiperidin-1-yl-methyl)-1,4-dioxaspiro[4.5]decaneand other known fungicidal active compounds are also known (cf. DE-OS(German Published Specification) 37 19 326).

However, the activity of the known fungicidal active compounds asindividual compounds, like that of the known synergistic combinations ofactive compounds, is however, in particular when small quantities arebeing used, not always completely satisfactory in all areas ofapplication.

It has now been found that the novel combinations of active compoundsconsisting of8-t-butyl-2-(N-ethyl-N-n-propylamino)-methyl-1,4-dioxaspiro[4.5]decaneof the formula (I) ##STR2## and at least

    (1) one azole derivative of the formula                                        ##STR3##                                                                      ##STR4##                                                                      ##STR5##                                                                      ##STR6##                                                                      ##STR7##                                                                     and/or at least                                                               (2) one azole derivative of the formula                                        ##STR8##                                                                      ##STR9##                                                                      ##STR10##                                                                     ##STR11##                                                                     ##STR12##                                                                     ##STR13##                                                                     ##STR14##                                                                     ##STR15##                                                                     ##STR16##                                                                     ##STR17##                                                                     ##STR18##                                                                     ##STR19##                                                                     ##STR20##                                                                     ##STR21##                                                                    R.sup.5 = CN                                                                  (FENBUCONAZOLE)                                                                ##STR22##                                                                    and/or                                                                        (3) the azole derivative of the formula                                        ##STR23##                                                                    and/or                                                                        (4) the azole derivative of the formula                                        ##STR24##                                                                    and/or                                                                        (5) the azole derivative of the formula                                        ##STR25##                                                                    and/or                                                                        (6) at least one azole derivative of the formula                               ##STR26##                                                                    R.sup.6 = CH.sub.3, R.sup.7 = CH.sub.3                                                                   (VII-1)                                            (METCONAZOLE)                                                                 R.sup.6 = H, R.sup.7 = CH(CH.sub.3).sub.2                                                                (VII-2)                                            (IPCONAZOLE)                                                                  and/or                                                                        (7) the azole derivative of the formula                                        ##STR27##                                                                    and/or                                                                        (8) at least one of the heterocycles of the formula                            ##STR28##                                                                    X = O, R.sup.8 = CH.sub.3, R.sup.9 = H, R.sup.10 = C.sub.10 H.sub.21                                     (IX-1)                                             (TRIDEMORPH)                                                                  X = O, R.sup.8 = CH.sub.3, R.sup.9 = H, R.sup.10 = C.sub.9 H.sub.19                                      (IX-2)                                             (ALDIMORPH)                                                                    ##STR29##                                                                     ##STR30##                                                                    and/or                                                                        (9) the compound of the formula                                                ##STR31##                                                                    and/or                                                                        (10) the compound of the formula                                               ##STR32##                                                                    and/or                                                                        (11) the compound of the formula                                               ##STR33##                                                                    and/or                                                                        (12) the compound of the formula                                               ##STR34##                                                                    and/or                                                                        (13) the compound of the formula                                               ##STR35##                                                                    and/or                                                                        (14) the compound of the formula                                               ##STR36##                                                                    and/or                                                                        (15) at least one of the compounds of the formula                              ##STR37##                                                                     ##STR38##                                                                     ##STR39##                                                                     ##STR40##                                                                    and/or                                                                        (16) at least one of the compounds of the formula                              ##STR41##                                                                    R.sup.12 = CH.sub.3        (XVII-1)                                           (PYRIMETHANIL)                                                                R.sup.12 = C.tbd.C--CH.sub.3                                                                             (XVII-2)                                           (MEPANIPYRIM)                                                                  ##STR42##                                                                    and/or                                                                        (17) at least one of the compounds of the formula                              ##STR43##                                                                    R.sup.13 = H               (XVIII-1)                                          (DICHLOFLUANID)                                                               R.sup.13 = CH.sub.3          (XVIII-2)                                        (TOLYFLUANID)                                                                 and/or                                                                        (18) the compound of the formula                                               ##STR44##                                                                    and/or                                                                        (19) the compound of the formula                                               ##STR45##                                                                    and/or                                                                        (20) the compound of the formula                                               ##STR46##                                                                    and/or                                                                        (21) the compound of the formula                                               ##STR47##                                                                    and/or                                                                        (22) the compound of the formula                                               ##STR48##                                                                    and/or                                                                        (23) the compound of the formula                                               ##STR49##                                                                    and/or                                                                        (24) the compound of the formula                                               ##STR50##                                                                    and/or                                                                        (25) the compound of the formula                                               ##STR51##                                                                    and/or                                                                        (26) at least one of the compounds of the formula                             Cl.sub.3 C--S--R.sup.14    (XXVII)                                             ##STR52##                                                                     ##STR53##                                                                    and/or                                                                        (27) the compounds of the formulae                                            3 Cu(OH).sub.2.CuCl.sub.2.x H.sub.2 O                                                                    (XXVIII-1)                                         and                                                                            ##STR54##                                                                    and/or                                                                        (28) the compound of the formula                                               ##STR55##                                                                    and/or                                                                        (29) the compound of the formula                                               ##STR56##                                                                    and/or                                                                        (30) the compound of the formula                                               ##STR57##                                                                    and/or                                                                        (31) the compound of the formula                                               ##STR58##                                                                    and/or                                                                        (32) the compound of the formula                                               ##STR59##                                                                    and/or                                                                        (33) the compounds of the formula                                              ##STR60##                                                                    X = F, Cl, Br, CH.sub.3                                                       n = 0, 1, 2, 3                                                                and/or                                                                        (34) the compound of the formula                                               ##STR61##                                                                    and/or                                                                        (35) at least one of the compounds of the formula                              ##STR62##                                                                    M = Zn                     (XXXVI-1)                                          (ZINEB)                                                                       M = Mn                     (XXXV)-2)                                          (MANEB)                                                                       (XXXVI-3) = Mixture of (XXXVI-1) and (XXXVI-2)                                (MANCOZEB)                                                                    and/or                                                                        (36) one compound of the formula                                               ##STR63##                                                                    Z = --S--S-- (THIRAM)      (XXXVII-1)                                         / = --S--Zn--S-- (ZIRAM)   (XXXVII-2)                                         and/or                                                                        (37) the compound of the formula                                               ##STR64##                                                                    and/or                                                                        (38) the compound of the formula                                               ##STR65##                                                                    and/or                                                                        (39) the compound of the formula                                               ##STR66##                                                                    and/or                                                                        (40) the compound of the formula                                               ##STR67##                                                                    and/or                                                                        (41) the compound of the formula                                              S.sub.x                    (XLII)                                             (WETTABLE SULPHUR)                                                            and/or                                                                        (42) at least one of the compounds of the formula                              ##STR68##                                                                      in which

R¹⁵ and R¹⁶, independently of each other, represent hydrogen, halogen,methyl or phenyl, and

R¹⁷ represents hydrogen or methyl,

possess very good fungicidal properties.

Surprisingly, the fungicidal effect of the combinations of activecompounds according to the invention is appreciably higher than the sumof the effects of the individual active compounds and also appreciablyhigher than the effects of the known combinations of active compounds.There thus exists a synergistic effect which could not have beenforeseen, and not simply a supplementation of the effect.

8-t-Butyl-2-(N-ethyl-N-n-propylamino)-methyl-1,4-dioxaspiro [4.5]decaneof the formula (I), and its employment as a fungicide, are known (cf.EP-OS (European Published Specification) 0 281 842).

The fungicidal components which are also present in the combinations ofactive compounds according to the invention are likewise known. Theactive compounds are described in detail in the following publications:

(1) compounds of the formula (II)

DE-OS (German Published Specification) 2 201 063

DE-OS (German Published Specification) 2 324 010

DE-OS (German Published Specification) 2 737 489

(2) compounds of the formula (III)

DE-OS (German Published Specification) 3 018 866

DE-OS (German Published Specification) 2 551 560

EP 47 594

DE 2 735 872

(3) compound of the formula (IV)

DE-OS (German Published Specification) 28 38 847

(4) compound of the formula (V)

EP 68 813

U.S. Pat. No. 4,496,551

(5) compound of the formula (VI)

DE-OS (German Published Specification) 2 429 523

DE-OS (German Published Specification) 2 856 974

U.S. Pat. No. 4,108,411

(6) compounds of the formula (VII)

EP 329 397

(7) Compound of the formula (VIII)

EP 183 458

(8) compounds of the formula (IX)

DD 140 041

(9) compound of the formula (X)

EP 382 375

(10) compound of the formula (XI)

EP 515 901

(11) compound of the formula (XII)

EP 314 422

(12) compound of the formula (XIII)

EP 49 854

(13) compound of the formula (XIV)

DE-OS (German Published Specification) 1 770 288

U.S. Pat. No. 3,869,456

(14) compound of the formula (XV)

DE 2 814 041

(15) compounds of the formula (XVI)

DE 2 207 576

U.S. Pat. No. 3,903,090

U.S. Pat. No. 3,755,350

U.S. Pat. No. 3,823,240

(16) compounds of the formula (XVII)

EP 270 111 and

EP 310 550

(21) compound of the formula (XXII)

EP 219 756

(37) compound of the formula (XXXVIII)

U.S. Pat. No. 4 512 989

(42) compounds of the formula (XLIII)

EP 398 692

Compounds from the groups (17), (18), (19), (20), (25), (26), (27),(28), (31), (34), (35), (36) and (41) are described, for example, in K.H. Buchel, "Pflanzenschutz und Schadlingsbekampfung (Plant Protectionand the Control of Pests), pages 121-153, Georg Thieme-Verlag,Stuttgart, 1977.

In addition to the active compound of the formula (I), the combinationsof active compounds according to the invention contain at least oneactive compound from the compounds of the groups (1) to (42). Inaddition to this, they can also contain further fungicidally activeadmixed components.

The synergistic effect is particularly apparent when the activecompounds in the combinations of active compounds according to theinvention are present in particular ratios by weight. However, theratios by weight of the active compounds in the combinations of activecompounds can be varied within a relatively wide range. In general 0.1to 10 parts by weight, preferably 0.3 to 3 parts by weight, of at leastone active compound from the groups (1) to (42) is/are allocated to 1part by weight of active compound of the formula (I).

The combinations of active compounds according to the invention possessvery good fungicidal properties. They can be employed, in particular,for controlling phytopathogenic fungi, such as Plasmodiophoromycetes,Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes,Deuteromycetes, etc.

The combinations of active compounds according to the invention areparticularly suited for controlling cereal diseases, such as Erysiphe,Cochliobolus, Septoria, Pyrenophora and Leptosphaeria, and for useagainst fungal infestation of vegetables, grapes and fruit, for exampleagainst Venturia or Podosphaera on apples, Uncinula on vine plants orSphaerotheca on cucumbers.

The high level of tolerance by plants of the combinations of activecompounds in the concentrations which are necessary for controllingplant diseases makes it possible to treat above-ground parts of plants,plant material and seeds, and the soil.

The combinations of active compounds according to the invention can beconverted into the customary formulations, such as solutions, emulsions,suspensions, powders, foams, pastes, granules, aerosols, very finecapsules in polymeric substances and in coating compositions for seeds,as well as ULV formulations.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is, emulsifying agents and/or dispersingagents, and/or foam-forming agents. In the case of the use of water asan extender, organic solvents can, for example, also be used asauxiliary solvents. As liquid solvents, there are suitable in the main:aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinatedaromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water. By liquefied gaseous extenders orcarriers are meant liquids which are gaseous at ambient temperature andunder atmospheric pressure, for example aerosol propellants, such ashalogenated hydrocarbons as well as butane, propane, nitrogen and carbondioxide. As solid carriers there are suitable: for example groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly-disperse silica, alumina and silicates. Assolid carriers for granules there are suitable: for example crushed andfractionated natural rocks such as calcite, marble, pumice, sepioliteand dolomite, as well as synthetic granules of inorganic and organicmeals, and granules of organic material such as sawdust, coconut shells,maize cobs and tobacco stalks. As emulsifying and/or foam-forming agentsthere are suitable: for example non-ionic and anionic emulsifiers, suchas polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates as well as albumen hydrolysis products. Asdispersing agents there are suitable: for example lignin-sulphite wasteliquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

The combinations of active compounds according to the invention can bepresent in the formulations as a mixture with other known activecompounds, such as fungicides, insecticides, acaricides and herbicides,and in mixtures with fertilizers or plant growth regulators.

The combinations of active compounds can be used as such or in the formof their formulations or the use forms prepared therefrom, such asready-to-use solutions, emulsifiable concentrates, emulsions,suspensions, wettable powders, soluble powders and granules.

They are used in a customary manner, for example by watering, spraying,atomizing, scattering, brushing on, dry dressing, moist dressing, wetdressing, slurry dressing or encrusting.

In the treatment of parts of plants, the active compound concentrationsin the use forms can be varied within a substantial range. They are, ingeneral, between 1 and 0.0001% by weight, preferably between 0.5 and0.001%.

In the treatment of seeds, amounts of active compound of 0.001 to 50 gper kilogram of seeds, preferably 0.01 to 10 g, are generally required.

For the treatment of the soil, active compound concentrations of 0.00001to 0.1% by weight, preferably of 0.0001 to 0.02% by weight, are requiredat the site of action.

The good fungicidal effect of the combinations of active compoundsaccording to the invention is evident from the examples below. While theindividual active compounds or the known combinations of activecompounds exhibit deficiencies in their fungicidal effect, it is clearlyevident from the tables of the following examples that the effect of thecombinations of active compounds according to the invention which hasbeen found is greater than the sum of the effects of the individualactive compounds and also greater than the effects of the knowncombinations of active compounds.

EXAMPLE 1

Erysiphe Test (wheat)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are dusted with spores of Erysiphe graminisf.sp. tritici.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%, in order to promotethe development of powdery mildew pustules.

Evaluation is carried out 7 days after the inoculation.

The active compounds, active compound concentrations and experimentalresults are shown in the following table.

                                      TABLE 1                                     __________________________________________________________________________    Erysiphe test (wheat)/protective                                                                           Active Degree of                                                              compound                                                                             effect in %                                                            concentration                                                                        of the                                                                 in the spray                                                                         untreated                                 Active compound              liquor in ppm                                                                        control                                   __________________________________________________________________________    known:                                                                         ##STR69##                   2      59                                        (I)                                                                            ##STR70##                   2      75                                        (II-1)                                                                        mixture according                                                             to the invention                                                              (I) + (II-I)                 1.5 + 0.5                                                                            100                                       3:1                                                                           __________________________________________________________________________

EXAMPLE 2

Erysiphe Test (barley)/curative

Solvent: 10 parts by weight of N-methyl-pyrrolidone

Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for curative activity, young plants are dusted with spores ofErysiphe graminis f. sp. hordei. 48 hours after the inoculation, theplants are sprayed with the preparation of active compound untildew-moist.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%, in order to promotethe development of powdery mildew pustules.

Evaluation is carried out 7 days after the inoculation.

The active compounds, active compound concentrations and experimentalresults are shown in the following table.

                                      TABLE 2                                     __________________________________________________________________________    Erysiphe test (barley)/curative                                                                                     Degree of                                                                     effect in %                                                          Active compound                                                                        of the                                                               concentration                                                                          untreated                               Active compound              in g/ha  control                                 __________________________________________________________________________    known:                                                                         ##STR71##                   40  20  12                                                                             88  75  66                              (I)                                                                            ##STR72##                   40  20  12                                                                             100   79  59                             ##STR73##                   40       96                                      (III-1)                                                                        ##STR74##                   12       50                                      (VI)                                                                           ##STR75##                   20       25                                      (IX-1)                                                                         ##STR76##                   20       79                                      (IX-4)                                                                         ##STR77##                   40       88                                      (XI)                                                                           ##STR78##                   20       63                                      (X)                                                                           known mixtures from DE-OS                                                     (German Published                                                             Specification) 37 19 326                                                       ##STR79##                   20 + 20  96                                      1:1                                                                            ##STR80##                   10 + 2   66                                      5:1                                                                           mixtures according to the invention                                           (I) + (III-1)                20 + 20  100                                     1:1                                                                           (I) + (II-1)                 10 + 2   84                                      5:1                                                                           (I) + (VI)                   10 + 2   84                                      5:1                                                                           (I) + (IX-1)                 10 + 10  79                                      1:1                                                                           (I) + (IX-4)                 10 + 10  88                                      1:1                                                                           (I) + (XI)                   20 + 20  100                                     1:1                                                                           (I) + (X)                    10 + 10  84                                      1:1                                                                           (I) + (III-4)                20 + 4   96                                      5:1                                                                           (I) + (III-4)                10 + 2   79                                      1:1                                                                           (I) + (VI)                   20 + 20  100                                     1:1                                                                           (I) + (III-2)                20 + 4   88                                      5:1                                                                           (I) + (XI)                   10 + 2   79                                      5:1                                                                           (I) + (X)                    20 + 4   75                                      5:1                                                                           __________________________________________________________________________

EXAMPLE 3

Erysiphe Test (wheat)/curative

Solvent: 10 parts by weight of N-methyl-pyrrolidone

Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for curative activity, young plants are dusted with spores ofErysiphe graminis f. sp. tritici. 48 hours after the inoculation, theplants are sprayed with the preparation of active compound untildew-moist.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%, in order to promotethe development of powdery mildew pustules.

Evaluation is carried out 7 days after the inoculation.

The active compounds, active compound concentrations and experimentalresults are shown in the following table.

                                      TABLE 3                                     __________________________________________________________________________    Erysiphe test (wheat)/curative                                                                                      Degree of                                                                     effect in %                                                          Active compound                                                                        of the                                                               concentration                                                                          untreated                               Active compound              in g/ha  control                                 __________________________________________________________________________    known:                                                                         ##STR81##                   40  20   73  73                                  (I)                                                                            ##STR82##                   40       73                                      (V)                                                                            ##STR83##                   20       55                                      (III-2)                                                                        ##STR84##                   40       77                                      (VI)                                                                           ##STR85##                   40       82                                      (IX-1)                                                                        mixtures according to the invention                                           (I) + (V)                    20 + 20  100                                     1:1                                                                           (I) + (VI)                   20 + 20  90                                      1:1                                                                           (I) + (III-2)                10 + 10  86                                      1:1                                                                           (I) + (IX-1)                 20 + 20  90                                      1:1                                                                           (I) + (IX-3)                 20 + 20  100                                     1:1                                                                           __________________________________________________________________________

EXAMPLE 4

Erysiphe Test (wheat)/protective

Solvent: 10 parts by weight of N-methyl-pyrrolidone

Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are dusted with spores of Erysiphe graminisf.sp. tritici.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%, in order to promotethe development of powdery mildew pustules.

Evaluation is carried out 7 days after the inoculation.

The active compounds, active compound concentrations and experimentalresults are shown in the following table.

                                      TABLE 4                                     __________________________________________________________________________    Erysiphe test (wheat)/protective                                                                                    Degree of                                                                     effect in %                                                          Active compound                                                                        of the                                                               concentration                                                                          untreated                               Active compound              in g/ha  control                                 __________________________________________________________________________    known:                                                                         ##STR86##                   40  12   75  11                                  (I)                                                                            ##STR87##                   40  12   75  60                                   ##STR88##                   40       70                                      (II-1)                                                                        known:                                                                         ##STR89##                   12       30                                      (IX-1)                                                                         ##STR90##                   20       40                                      (V)                                                                           known mixture from DE-OS                                                      (German Published                                                             Specification) 37 19 326                                                       ##STR91##                   20 + 20  75                                      mixtures according to the invention                                           (I) + (II-1)                 20 + 20  85                                      1:1                                                                           (I) + (IX-1)                 10 + 2   70                                      5:1                                                                           (I) + (V)                    10 + 10  90                                      1:1                                                                           __________________________________________________________________________

EXAMPLE 5

Podosphaera Test (apple)/protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkyl-aryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are inoculated by dusting with conidiaof the causative organism of apple mildew Podosphaera leucotricha.

The plants are then placed in a greenhouse at 23° C. and a relativeatmospheric humidity of about 70%.

Evaluation is carried out 10 days after the inoculation.

Active compounds, active compound concentrations and experimentalresults are shown in the following table.

                                      TABLE 5                                     __________________________________________________________________________    Podosphaera test (apple)/protective                                                                                 Degree of                                                            Active compound                                                                        effect in % of                                                       concentration in                                                                       the untreated                           Active compound              ppm      control                                 __________________________________________________________________________    known:                                                                         ##STR92##                                                                    (I)                                                                            ##STR93##                                                                     ##STR94##                                                                    (II-1)                                                                        known from DE-OS 37 19 326:                                                    ##STR95##                   (5:1)  0.5 + 0.1                                                                       55                                      5:1                                                                           mixture according to the invention:                                           (I) + (II-1)                 0.5 + 0.1                                                                              86                                      5:1                                                                           __________________________________________________________________________

It is understood that the specification and examples are illustrativebut not limitative of the present invention and that other embodimentswithin the spirit and scope of the invention will suggest themselves tothose skilled in the art.

What is claimed is:
 1. A fungicidal composition comprising a synergisticfungicidally effective amount of a combination of:(A)8-t-butyl-2-(N-ethyl-N-n-propylamino)-methyl-1,4-dioxaspiro[4.5]-decaneof the formula ##STR96## and (B) a compound of the formula ##STR97##wherein the weight ratio of (A):(B) is between about 1:0.1 and 1:10. 2.A composition according to claim 1, wherein the weight ratio of (A):(B)is between about 1:0.3 and 1:3.
 3. A method of combating fungi whichcomprises administering to such fungi or to a fungus habitat asynergistic fungicidally effective amount of a composition according toclaim 1.